New polyfluorinated aromatic and aza-aromatic diselenides, selenyl chlorides, non-symmetric selenides and selenoxides

Article abstract of DOI:10.1016/j.jfluchem.2012.08.002

New polyfluorinated ArSeSeAr, ArSeCl (Ar = 4-RC₆F ₄-1-yl, 5-HC₅F₃N-3-yl), non-symmetric ArSeAr' (Ar = 4-RC₆F₄-1-yl, Ar' = 4-NC₅F ₄-1-yl) and non-symmetric, i.e. chiral

Full text of DOI:10.1016/j.jfluchem.2012.08.002

Journal of Fluorine Chemistry 144 (2012) 118–123
Contents lists available at SciVerse ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
New polyfluorinated aromatic and aza-aromatic diselenides, selenyl chlorides,
non-symmetric selenides and selenoxides
Arkady G. Makarov, Alexander Yu. Makarov, Irina Yu. Bagryanskaya, Makhmut M. Shakirov,
*
Andrey V. Zibarev
Institute of Organic Chemistry, Russian Academy of Sciences, 630090 Novosibirsk, Russia
A R T I C L E I N F O
A B S T R A C T
Article history:
New polyfluorinated Ar–Se–Se–Ar, Ar–Se–Cl (Ar = 4-RC6F4-1-yl, 5-HC5F3N-3-yl), non-symmetric Ar–Se–
Ar0 (Ar = 4-RC6F4-1-yl, Ar0 = 4-NC5F4-1-yl) and non-symmetric, i.e. chiral, Ar–Se(55O)–Ar0 (Ar = Ar = 4-
RC6F4-1-yl, Ar0 = 4-NC5F4-1-yl) derivatives, as well as (4-NC5F4-1-yl)SeNa, were prepared and
characterized by single-crystal X-ray diffraction and multinuclear NMR (1H, 13C, 14N, 19F, 77Se).
ß 2012 Elsevier B.V. All rights reserved.
Received 19 July 2012
Received in revised form 14 August 2012
Accepted 16 August 2012
Available online 23 August 2012
Keywords:
Aza-aromatics
Aromatics
Diselenides
Organofluorine
Selenides
Selenoxides
Selenyl chlorides
Synthesis
1. Introduction
2. Results and discussion
Aromatic selenium compounds, particularly diselenides, sele-
nyl chlorides, selenolates and selenoxides, are versatile reagents in
organic, organoelement and main group chemistry [1,2]. Their
polyfluorinated congeners, especially non-symmetric (where
possible), are studied to much lesser extent [3,4]. At the same
time they are of interest to fundamental chemistry [1–5] and its
applications to the materials science [5–9].
In this work we report on preparation and characterization of
new polyfluorinated Ar–Se–Se–Ar, Ar–Se–Cl (Ar = 4-RC6F4-1-yl, 5-
HC5F3N-3-yl), non-symmetric Ar–Se–Ar0 (Ar = 4-RC6F4-1-yl,
Ar0 = 4-NC5F4-1-yl) and non-symmetric, i.e. chiral, Ar–Se(55O)–
Ar0 (Ar = 4-RC6F4-1-yl, Ar0 = 4-NC5F4-1-yl) derivatives, as well as
selenolate (4-NC5F4-1-yl)SeNa (Chart 1). The compounds synthe-
sized were characterized by multinuclear (1H, 13C, 14N, 19F, 77Se)
NMR, and compounds 3, 5, 9, 12 and 14 by single-crystal X-ray
diffraction (XRD).
The diselenides 1–5 were obtained from corresponding arenes
by three-step one-pot procedure (Scheme 1). The isolated yields
varied from 24% (5) to 77% (3). The structures of 3 and 5 were
confirmed by XRD (Fig. 1; Supporting Information, Fig. S1).
The selenyl chlorides 6–9 were synthesized from the corre-
sponding diselenides 1, 2, 4 and 5 in practically quantitative
isolated yields by the action of elemental chlorine (Scheme 2). The
structure of compound 9 was confirmed by XRD (Fig. 2; Supporting
Information, Fig. S2). Diselenide 3 under action of either chlorine or
SO2Cl2 produced only complex mixture of unidentified com-
pounds. In the context of compounds 4, 5, 8 and 9, it should be
noted that they represent rather rare functional derivatives of
2,3,4,6-tetrafluoropyridine [10], furthermore first Se-containing
derivatives.
Polyfluorinated diselenides are suitable precursors of corre-
sponding selenolates which are useful reagents and ligands [5].
Attempt of reduction of C6F5–Se–Se–C6F5 (15) with Ph3P/H2O in
pyridine (the method is known to perform well for C6H5–X–X–
C6H5, X = Se, S [11]) was unsuccessful, only Ph3P = Se (identified by
XRD in full agreement with previous results [12]) and a mixture of
unidentified products were isolated. Reduction of 1 and 15 with
NaBH4 allowed however preparing of corresponding selenolates
trapped by pentafluoropyridine to give non-symmetric selenides
* Corresponding author. Fax: +7 383 330 9752.
E-mail address: zibarev@nioch.nsc.ru (A.V. Zibarev).
0022-1139/$ – see front matter ß 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2012.08.002

A.G. Makarov et al. / Journal of Fluorine Chemistry 144 (2012) 118–123
119
F
F
F
F
F
Cl
SeCl
SeCl
Cl
Se Se
Cl
Se
10
N
F
F
1
6
MeO
Se Se
OMe
F
MeO
Cl
Se
11
N
F
F
2
7
N
SeNa
F
F
F
Me2N
Se Se
NMe2
12
3
H
H
H
O
F
SeCl
SeCl
Se
N
N
F
F
F
F
F
F
F
F
Se Se
N
N
N
N
N
N
13
8
4
O
F
Cl
Se
Se Se
14
5
9
Chart 1. Compounds synthesized.
Molecular and crystal structures of compound 14 confirmed by
XRD (Fig. 3; Supporting Information, Fig. S3) are very similar to
those of C6F5Se(55O)C6F5 [13].
3. Conclusions
Synthetic protocols for preparation of new polyfluorinated
aromatic and aza-aromatic Ar–Se–Se–Ar, Ar–Se–Cl (Ar = 4-RC6F4-
1-yl, 5-HC5F3N-3-yl), non-symmetric Ar–Se–Ar0 (Ar = 4-RC6F4-1-
yl, Ar0 = 4-NC5F4-1-yl) and non-symmetric, i.e. chiral, Ar–Se(55O)–
Ar0 (Ar = 4-RC6F4-1-yl, Ar0 = 4-NC5F4-1-yl) derivatives are elabo-
rated. Compounds 4, 5, 8 and 9 represent first Se-containing
derivatives of 2,3,4,6-tetrafluoropyridine. The compounds synthe-
sized can be used as reagents and ligands in organoelement, main
group and coordination chemistry.
Scheme 1. Synthesis of the diselenides 1–5.
10 and 11 in the isolated yields of 42 and 85%, respectively (Scheme
3). From the preparation of compound 10, selenolate (4-NC5F4-1-
yl)SeNa (12) was unexpectedly isolated as minor by-product
identified by XRD in the form of 12ꢀ3H2O after crystallization from
wet acetone (Fig. 3).
4. Experimental
4.1. General
The selenides 10 and 11 were converted to non-symmetric, i.e.
chiral, selenoxides 13 and 14 by oxidation with KMnO4 in acetic
acid with isolated yields of 39 and 77%, respectively (Scheme 4).
Other oxidizers tried including 3-chloroperbenzoic acid (cf. [13]),
H2O2 (30%) and HNO3 (100%) were not effective Fig. 4.
The 1H, 13C, 14N and 77Se NMR spectra were measured with a
Bruker AV-600 spectrometer at the frequencies of 600.1, 151.0,
43.4 and 114.5 MHz, respectively, and the 19F NMR spectra with a
Bruker AV-300 spectrometer at the frequency of 282.4 MHz, for
@
˚
Fig. 1. XRD molecular structures of compounds 3 and 5 (displacement ellipsoids at 30%). Selected bond lengths (A), bond and torsion angles ( ): Compound 3: C–Se 1.899(5)
and 1.907(5), Se–Se 2.3385(12); C–Se–Se 101.8(2) and 100.45(19); C–Se–Se–C ꢁ106.52. Compound 5: C–Se 1.914(4) and 1.911(4), Se–Se 2.3192(8); C–Se–Se 99.71(12) and
100.13(12); C–Se–Se–C ꢁ79.44(17).

120
A.G. Makarov et al. / Journal of Fluorine Chemistry 144 (2012) 118–123
F
R
SeCl
F
F
R
Se Se
Se Se
R
R = Cl (6), CH3O (7)
Cl2
R
R
R
F
F
F
SeCl
R = H (8), F (9)
Scheme 2. Synthesis of the selenyl chlorides 6–9.
N
N
N
solutions in CDCl3 unless otherwise indicated. Chemical shifts (
are given with respect to TMS (1H, 13C), NH3 (liq.) (14N), C6F6 (19F),
and Se(CH3)2
77Se).
d)
Fig. 2. XRD molecular structure of compound 9 (displacement ellipsoids at 30%).
(
@
˚
Selected bond lengths (A), bond and torsion angles ( ) (two crystallographically
High-resolution mass spectra (EI, eV) of compounds 1–5, 10 and
11 were taken with a Termo Scientific DFS mass spectrometer with
direct inlet and source temperature 160 8C. Electrospray ionization
(ESI) mass spectra of compounds 13 and 14 were obtained with a
Bruker Daltonik micrOTOF-Q hybrid quadrupole time-of-flight
mass-spectrometer equipped with electrospray ionization source,
for MeOH solutions, with nitrogen as drying gas. ESI-MS
conditions: positive scan in the range m/z = 80–3000,
Vcap = 4500 V, drying gas flow and temperature 4.0 L/min and
190 8C, nebylizer pressure 1.0 bar. A small syringe pump was used
for the introduction of solution samples directly to spray chamber
independent molecules): C–Se 1.904(4) (in both molecules), Se–Cl 2.1877(11) and
2.1859(11); C–Se–Cl 95.85(11) and 95.47(11); (N–)C–C–Se–Cl 114.9(3) and
117.5(3).
of the mass-spectrometer, flow rate was 2
mL/min. For selenyl
chlorides 6–9 mass spectra were not obtained due to instability of
the compounds under MS conditions.
UV–vis spectra were recorded with HP 8453 spectrophotome-
ter for heptane solutions.
The solvents were dried with common drying agents. The
reaction solvents were distilled off under reduces pressure.
Starting 2,3,5,6-tetrafluoro-1-chlorobenzene [14], 2,3,5,6-tet-
rafluoroanisole [15], N,N-dimethyl-2,3,5,6-tetrafluoroaniline [16],
2,4,6-trifluoropyridine and 2,3,4,6-tetrafluoropyridine [17], and
pentafluoropyridine [18] were described before.
Fig. 3. XRD molecular structure of 12ꢀ3H2O (displacement ellipsoids at 30%).
ꢂ
˚
Selected bond lengths (A) and bond angles (8): C–Se 1.8853(16), Se Na 3.2068(9),
NaꢂꢂO 2.3957(16), 2.4123(17), 2.4010(17), 2.4646(15) and 2.3344(19); C–Se–Na
114.51(5).
Tables 1–4 contain NMR, XRD, physical, spectral and analytical
data of the compounds synthesized.
4.2. X-ray diffraction
4.3. Preparations
The XRD data for 3, 5 and 9 were collected on a Bruker P4
4.3.1. Diselenides 1–5
diffractometer with
u
/2
u
scans, and for 12 and 14 on a Bruker
At ꢁ60 8C and under argon, 40 mmol of n-BuLi (2.5 M solution
in hexanes) was added dropwise to a stirred solution of 40 mmol of
corresponding (aza)arene in 100 ml of Et2O. After additional
30 min., 3.16 g (40 mmol) of finely ground elemental Se was added
by small portions. After additional 2 h, the reaction mixture was
slowly warmed to ꢁ55 (4), ꢁ30 (5), or ꢁ10 8C (1–3), and 5.08 g
(20 mmol) of elemental iodine was added. After additional 30 min.,
the reaction mixture was warmed to ambient temperature and
excess of aqueous Na2S2O3 was slowly added. The organic and
water layers were separated, and the latter was extracted with
Et2O (2–4) or CHCl3 (1). Combined organic solution was dried with
MgSO4, filtered and evaporated. The residue was crystallized from
hexane (1–3, 5) or its 2:1 mixture with chloroform (4). In the case
of 1 and 5, chromatography on silica column was employed before
crystallization, eluent hexane/benzene 20:1. Compounds 2 and 5
were additionally purified by sublimation at 140 8C/8 mm and
80 8C/2 mm, respectively. Compounds 1, 2, 4, 5 were obtained in
Kappa Apex II CCD diffractometer with
˚
a (l = 0.71073 A) radiation with a graphite
w, v scans of narrow (0.58)
frames, using Mo K
monochromator. Absorption corrections for 5 were applied by
integration taking into account real crystal shape; those for 3 and 9
were applied by empirical methods based on
c scans, and for 12
and 14 using the SADABS program. The structures were solved by
direct methods using the SHELXS-97 program and refined by the
least-squares method in the full-matrix anisotropic (isotropic for H
atoms) approximation using the SHELXL-97 program [19]. The H
atoms positions for 3 were calculated with the riding model and for
12 located from difference Fourier map. The obtained structures
were analyzed with the PLATON [20] and MERCURY [21] programs.
Atomic coordinates, thermal parameters, bond lengths and
bond angles have been deposited at the Cambridge Crystallo-
graphic Data Center as CCDC-891650 (3), ꢁ891651 (5), ꢁ891652
(9), ꢁ891653 (12) and ꢁ891654 (14).
Scheme 3. Synthesis of compounds 10 and 11.

A.G. Makarov et al. / Journal of Fluorine Chemistry 144 (2012) 118–123
121
O
Se
KMnO4
CH3COOH
R
F
Se
F
N
R
F
F
N
10
11
13 14
R = F ( ), Cl ( )
R = F ( ) , Cl (
)
Scheme 4. Synthesis of compounds 13 and 14.
the form of yellow prisms or needles, and compound 3 in the form
of red needles.
4.3.2. Selenyl chlorides 6–9
At ambient temperature, excess of elemental chlorine was
slowly passed through stirred solution of 1 mmol of corresponding
diselenide (1, 2, 4, 5) in 10 ml of CCl4. The solvent was distilled off.
Compounds 6–9 were obtained in the form of dark-red oil, which in
the case of compounds 8 and 9 crystallized below 4 8C in deep-red
plates.
Fig. 4. XRD molecular structure of compound 14 (displacement ellipsoids at 30%).
˚
Selected bond lengths (A) and bond angles (8) (three crystallographically
independent molecules): C–Se 1.975(9) and 1.966(8), 1.967(9) and 1.953(8),
1.964(10) and 1.974(9), Se–O 1.647(7), 1.645(7) and 1.656(7); C–Se–O 104.7(4) and
105.0(3), 104.8(4) and 104.3(4), 101.8(4) and 104.5(4), C–Se–C 92.3(4), 95.7(4) and
96.2(4).
Table 1
NMR chemical shifts,
d
, for compounds.a
13C
19F
77Se
1
2
147.0, 143.6, 115.2, 106.8
36.8, 23.2
377
367
371
352
372
809
809
795
806
180
187
927
932
147.5, 140.6, 140.2, 100.3, 62.0
34.3, 5.6
3
147.7, 140.7, 133.5, 97.0, 42.8
32.8, 11.1
4
173.2, 163.6, 162.4, 97.5, 95.9
107.0, 100.5, 82.8
102.9, 81.6, 62.1, ꢁ1.6
39.4, 24.0
5
160.2, 155.1, 151.2, 132.8, 98.8
6
146.5, 143.8, 117.5, 107.9
7
147.3, 142.7, 140.0, 101.2, 61.9
37.2, 6.0
8
173.0, 165.0, 162.2, 99.2, 96.3
109.7, 104.2, 85.9
105.6, 84.9, 65.4, ꢁ1.1
72.6, 36.8, 29.2, 14.1, 3.2
72.7, 36.4, 29.6, 23.9
75.1, 26.3, 23.1, 17.7, 5.1
75.3, 26.1, 23.2c
9
160.0, 154.9, 152.6, 132.9, 100.5
147.1, 143.2, 143.1, 141.2, 137.6, 122.0, 98.1
146.7, 144.0, 143.2, 141.2, 121.8, 115.7, 102.1
146.0, 144.7, 143.6, 140.9, 138.1, 132.6, 114.3
145.6, 144.6, 143.6, 140.9, 132.5, 128.8, 118.4
10
11
13b
14b
a
1H: 2: 4.13; 3: 3.05; 4: 6.69, 7 4.19; 8: 6.74. 14N: 3: 39; 4: 237; 8: 238; 9: 237.
In CH2Cl2/C6D6.
b
c
Relative integral intensities of peaks are 2:4:2.
Table 2
XRD data for compounds.
Compound
3
5
9
12 3H2O
14
Formula
C16H12F8N2Se2
542.20
C10F8N2Se2
458.04
C5ClF4NSe
264.47
C5H6F4NSeO3Na
306.05
C11ClF8NOSe
428.53
Molecular weight
Temperature, K
Syngony
293
296
200
200
200
Monoclinic
P21/c (No. 14)
15.354(3)
7.9550(16)
17.029(3)
90
Monoclinic
P21/n (No. 14)
5.2916(5)
17.8512(15)
13.6042(15)
90
Monoclinic
P21/c (No. 14)
23.9579(15)
7.2127(6)
8.7725(8)
90
Triclinic
Triclinic
Space group
P ꢁ 1 (No. 2)
6.1763(4)
7.5180(5)
11.0469(8)
107.125(2)
95.469(2)
96.683(2)
482.32(6)
2
P-1 (No. 2)
10.8044(11)
14.3303(18)
14.5808(18)
116.766(3)
99.675(4)
96.025(4)
1944.7(4)
6
˚
a (A)
˚
b (A)
˚
c (A)
a
b
g
(8)
(8)
(8)
116.62(3)
90
93.834(7)
90
100.383(6)
90
3
˚
V (A )
1859.5(8)
4
1282.2(2)
4
1491.1(2)
8
Z
Dcalc. (g/cm3)
1.937
2.373
2.356
2.107
1.905
F(000)
m
1048
856
992
296
1074
(mmꢁ1
)
4.058
5.861
5.403
3.985
2.163
Crystal size (mm)
range(8)
Indices
0.40 ꢃ 0.20 ꢃ 0.10
2.4–27.5
0.90 ꢃ 0.10 ꢃ 0.06
1.9–28.0
0.40 ꢃ 0.30 ꢃ 0.20
2.6–28.0
0.50 ꢃ 0.30 ꢃ 0.04
2.0–32.5
ꢁ8 ꢄ h ꢄ 9,
ꢁ11 ꢄ k ꢄ 11,
ꢁ16 ꢄ l ꢄ 16
16338
0.55 ꢃ 0.35 ꢃ 0.20
1.6–27.1
ꢁ13 ꢄ h ꢄ 13,
ꢁ18 ꢄ k ꢄ 18,
ꢁ18 ꢄ l ꢄ 18
54431
u
ꢁ19 ꢄ h ꢄ 0,
0 ꢄ k ꢄ 10,
ꢁ19 ꢄ l ꢄ 22
4365
ꢁ6 ꢄ h ꢄ 0,
ꢁ23 ꢄ k ꢄ 0,
ꢁ17 ꢄ l ꢄ 17
3204
ꢁ31 ꢄ h ꢄ 31,
0 ꢄ k ꢄ 9,
0 ꢄ l ꢄ 11
3840
Collected reflections
Independent reflections
4209 (Rint = 0.032)
2589
3085 (Rint = 0.059)
2007
3600 (Rint = 0.024)
2774
3250 (Rint = 0.042)
3053
8531 (Rint = 0.043)
7053
Reflections [I > 2
Completeness to
Abs. correction
s
u
(I)]
(%)
98.4
100.0
99.5
93.0
99.4
Empirical
0.53/0.85
4209/0/253
1.03
Integration
0.52/0.71
3085/0/199
1.03
Empirical
0.77/0.99
3600/0/217
1.09
Empirical
0.52/0.75
3250/6/136
1.11
Empirical
0.38/0.67
8531/0/622
1.18
Min./max. Transmitance
Data/restrains/parameters
Goodness of fit on F2
Final R indices [I > 2
s
(I)]
R1 = 0.0488, wR2 = 0.1091
R1 = 0.0896, wR2 = 0.1306
R1 = 0.0441, wR2 = 0.0896
R1 = 0.0810, wR2 = 0.1044
R1 = 0.0402, wR2 = 0.0967
R1 = 0.0594, wR2 = 0.1059
R1 = 0.0199, wR2 = 0.0474 R1 = 0.0648, wR2 = 0.2180
R1 = 0.0224, wR2 = 0.0537 R1 = 0.0779, wR2 = 0.2292
R indices (all data)

122
A.G. Makarov et al. / Journal of Fluorine Chemistry 144 (2012) 118–123
Table 3
to eluate. The resulted mixture was extracted with ethylacetate.
Organic layer was separated, dried with MgSO4, filtered and
evaporated. Compound 14 was obtained in the form of white
powder. Single crystals of 14 suitable to XRD were prepared by
slow evaporation of CH2Cl2 solution.
Isolated yields, melting points, and MS and UV–vis data for compounds.a,b
Compound
Yield, %
M.p., 8C
MS, m/z, found/calc.
1
2
51
57
77
68
24
95
92
90
92
42
85
39
77
100–102
73–74
79–81
106–108
88–90
Oil
521.7591/521.7596
517.8569/517.8570
543.9203/543.9203
423.8450/423.8453
459.8255/459.8264
–
3
4
Acknowledgments
5
6
The authors are grateful to Prof. Dr. Yuri V. Gatilov for valuable
discussion of the XRD structures, to Dr. Vladimir I. Rodionov, Mr.
AlexanderM. Maksimov andMr. Pavel V.Nikulshinfortheirgenerous
gifts of the starting materials, to Prof. Dr. Valentina P. Fadeeva for
elemental analysis for Se, and to the Collective Chemical Service
Center of Siberian Branch of the Russian Academy of Sciences for
instrumental facilities. A. G. M. thanks the Russian Science Support
Foundation for a 2010–2011 Postgraduate Scholarship.
7
Oil
–
8
45–47
28–30
29–30
66–67
144–146
142–143
–
9
–
10
11
13
14
394.9055/394.9060
410.8754/410.8765
435.888/435.889c
429.878/429.878d
a
UV–vis,
l, nm (lg e): 1: 242 (4.06), 264 (4.10), 348 (3.12); 2: 201 (4.31), 219
(4.13), 276 (4.06), 343 (3.21); 3: 226 (4.25), 249 (4.21), 326 (4.19); 4: 265 (4.03), 345
(2.94); 5: 273 (4.12), 346 (2.78).
b
MS: 78Se for 1, 10 and 11, 80Se for other compounds, except 6–9 for which mass
Appendix A. Supplementary data
spectra were not obtained due to their instability under experimental conditions.
c
[M +Na]+.
[M + H]+.
d
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.jfluchem.2012.08.002.
Table 4
References
Analytical data for compounds.
[1] (a) T. Wirth (Ed.), Organoselenium Chemistry. Synthesis and Reactions, Wiley-
VCH, 2011;
Compound
Found/calculated, %
(b) A.J. Mukherjee, S.S. Zade, H.B. Singh, R.B. Sinoj, Chemical Reviews 110 (2010)
4357–4416;
C
H
N
F
1
2
24.99/24.64
32.38/32.58
35.57/35.44
28.39/28.46
25.89/26.22
24.34/24.19
28.46/28.65
24.56/24.36
22.76/22.71
33.64/33.36
32.17/32.03
32.53/32.06
30.72/30.83
–
4.53/4.79
–
25.55/25.98
29.46/29.45
29.12/28.03
27.16/27,01
33.01/33.18
25.63/25.51
25.74/25.89
23.52/23.12
29.10/28.73
43.58/43.17
36.30/36.84
41.04/41.49
35.47/35.47
(c) D.M. Freudendahl, T. Wirth, in: J.D. Woollins, R.S. Laitinen (Eds.), Selenium and
Tellurium Chemistry From Small Molecules to Biomolecules and Materials,
Springer, 2011, pp. 41–56;
(d) F. Devillanova (Ed.), Handbook of Chalcogen Chemistry, Royal Society of
Chemistry, 2006.
1.12/1.17
3
2.30/2.23
5.16/5.17
6.63/6.64
6.18/6.12
–
4
0.67/0.48
5
–
[2] (a) A.G. Makarov, I.Yu. Bagryanskaya, Yu.V. Gatilov, N.V. Kuratieva, A.Yu.
Makarov, M.M. Shakirov, A.V. Alexeyev, K. Tersago, C. Van Alsenoy, F. Blockhuys,
A.V. Zibarev, European Journal of Inorganic Chemistry (2010) 4801–4810;
(b) K. Tersago, I.Yu. Bagryanskaya, Yu.V. Gatilov, S.A. Gromilov, A.Yu. Makarov, M.
Mandado, C. Van Alsenoy, A.V. Zibarev, F. Blockhuys, European Journal of Inor-
ganic Chemistry (2007) 1958–1965;
6
–
7
1.29/1.03
–
8a
9
0.65/0.41
5.74/5.68
5.01/5.30
3.77/3.54
3.73/3.40
3.71/3.40
3.25/3.27
–
–
–
–
–
10b
11a
13
14
(c) A.Yu. Makarov, E. Lork, R. Mews, A.V. Zibarev, Journal of Fluorine Chemistry
127 (2006) 437–442;
(d) K. Tersago, M. Mandado, C. Van Alsenoy, I.Yu. Bagryanskaya, M.K. Kovalev,
A.Yu. Makarov, Yu.V. Gatilov, M.M. Shakirov, A.V. Zibarev, F. Blockhuys, Chemical
European Journal 11 (2005) 4544–4551;
(e) A.Yu. Makarov, I.G. Irtegova, N.V. Vasilieva, I.Yu. Bagryanskaya, T. Borrmann,
Yu.V. Gatilov, E. Lork, R. Mews, W.D. Stohrer, A.V. Zibarev, Inorganic Chemistry 44
(2005) 7194–7199.
a
Cl: 6 23.32/23.80; 7 11.87/12.08; 8, 14.27/14.38; 11, 8.59/8.59.
Se: 7 26.70/26.90; 10, 20.10/19.94, 11 19.40/19.14.
b
4.3.3. Selenides 10, 11 and selenolate 12
[3] (a) T.M. Klapoetke, B. Krumm, P. Meyer, Zeitschrift fu¨r Naturforschung B 59
(2004) 547–553;
At ambient temperature and under argon, 38 mg (1 mmol) of
NaBH4 was added in small portions to a stirred solution of
0.5 mmol of 15 in 10 ml of ethanol or to solution of the same
amount of 1 in 10 ml of its 1:1 mixture with Et2O. After additional
5 min., solution of 200 mg (1.2 mmol) of C5F5N in 1 ml of ethanol
was added. (a) The solvent was distilled off, and the residue
extracted with hexane. Extract was evaporated and the residue
sublimed at 30 8C/1 mm. The product was crystallized from
ethanol at ꢁ20 8C. Compound 10 was obtained as white powder.
Very minor reaction residue insoluble in hexane was crystallized
from wet acetone. Compound 12ꢀ3H2O was obtained in the form of
colorless crystals suitable to XRD. (b) The solvent was distilled off,
and the residue crystallized from hexane at ꢁ20 8C. Compound 11
was obtained as white powder.
(b) T.M. Klapoetke, B. Krumm, K. Polborn, European Journal of Inorganic Chem-
istry (1999) 1359–1366.
[4] A.Yu. Makarov, K. Tersago, K. Nivesanond, F. Blockhuys, C. Van Alsenoy, M.K.
Kovalev, I.Yu. Bagryanskaya, Yu.V. Gatilov, M.M. Shakirov, A.V. Zibarev, Inorganic
Chemistry 45 (2006) 2221–2228.
[5] (a) T.J. Emge, M.D. Romanelli, B.F. Moore, J.G. Brennan, Inorganic Chemistry 49
(2010) 7304–7312;
(b) A.L. Fuller, F.R. Knight, A.M.Z. Slawin, J.D. Woollins, European Journal of
Inorganic Chemistry (2010) 4034–4043.
[6] (a) P. Howes, M. Green, C. Johnston, A. Crossley, Journal of Materials Chemistry 18
(2008) 3474–3480;
(b) A.M.M. Abeykoon, M. Castro-Colin, E.V. Anokhina, M.N. Iliev, W. Donner, A.J.
Jacobson, S.C. Moss, Physical Review B 77 (2008) 075333/1;
(c) G. Kedarnath, L.B. Kumbhare, V.K. Jain, A. Wadawale, G.K. Dey, C. Thinaharan,
S. Naveen, M.A. Sridhar, J.S. Prasad, Bulletin of the Chemical Society of Japan 81
(2008) 489–494;
(d) A. Dass, R. Guo, J.B. Tracy, R. Balasubramanian, A.D. Douglas, R.W. Murray,
Langmuir 24 (2008) 310–315;
(e) J.G. Brennan, T. Siegrist, P. Caroll, S. Stuczynski, L. Brus, M.L. Steigerwald,
Journal of the American Chemical Society 111 (1989) 4141–4143;
(f) J.G. Brennan, T. Siegrist, S. Stuczynski, P. Carroll, P. Rynders, L.E. Brus, M.L.
Steigerwald, Chemistry of Materials 2 (1990) 403–409.
[7] (a) O.P. Dimitriev, N.A. Ogurtsov, A.A. Pud, P.S. Smertenko, Yu.P. Piryatinski, Yu.V.
Noskov, A.S. Kutsenko, G.S. Shapoval, Journal of Physical Chemistry C 112 (2008)
14745–14753;
4.3.4. Selenoxides 13 and 14
At ambient temperature, 110 mg (0.7 mmol) of KMnO4 were
added in small portions to a stirred solution of 0.2 mmol of 10 or 11
in 5 ml of glacial acetic acid. After additional 30 min, (a) the solvent
was distilled off and the residue sublimed at 110 8C/1 mm.
Compound 13 was obtained in the form of white powder. (b)
The reaction mixture was passed through short silica column
(eluent: ethylacetate), and saturated aqueous NaHCO3 was added
(b) F. Aslam, D.M. Graham, D.J. Binks, P. Dawson, N. Pickett, P. O’Brien, C.C. Byeon,
D.-K. Ko, J. Lee, Journal of Applied Physics 103 (2008) 093702–093707;
(c) A.V. Firth, Y. Tao, D. Wang, J. Ding, F. Bensebaa, Journal of Materials Chemistry
15 (2005) 4367–4372;

A.G. Makarov et al. / Journal of Fluorine Chemistry 144 (2012) 118–123
123
(d) G. Kedarnath, S. Dey, V.K. Jain, G.K. Dey, B. Varghese, Polyhedron 25 (2006)
2383–2391.
(b) M. Sakakibara, K. Katsumata, Y. Wanatabe, T. Toru, Y. Ueno, Synthesis
(1992) 377–379;
[8] (a) A. Eichhoefer, O. Hampe, M. Blom, European Journal of Inorganic Chemistry
(2003) 1307–1314;
(c) L.E. Overman, J. Smoot, J.D. Overman, Synthesis (1974) 59–60.
[12] P.W. Codding, K.A. Kerr, Acta Crystallographica B 35 (1979) 1261–1263.
[13] T.M. Klapoetke, B. Krumm, P. Mayer, H. Piotrowski, O.P. Ruscitti, Zeitschrift fur
Naturforschung B57 (2002) 145–150.
(b) V.N. Soloviev, A. Eichhoefer, D. Fenske, U. Banin, Journal of the American
Chemical Society 123 (2001) 2354–2364;
(c) V.N. Soloviev, A. Eichhoefer, D. Fenske, U. Banin, Journal of the American
Chemical Society 122 (2000) 2673–2674;
[14] V.E. Platonov, A.M. Maksimov, K.V. Dvornikova, P.V. Nikulshin, Russian Journal of
Organic Chemistry 41 (2005) 1647–1653.
(d) M.W. DeGroot, C. Khadka, H. Roesner, J.F. Corrigan, Journal of Cluster Science
17 (2006) 97–110;
(e) A. Eichhoefer, European Journal of Inorganic Chemistry (2005) 1245–1253.
[9] (a) X. Huang, J. Li, Journal of the American Chemical Society 129 (2007)
3157–3162;
[15] R.D. Chambers, D.J. Spring, Tetrahedron 27 (1971) 669–680.
[16] J. Burdon, W.B. Hollyhead, J.C. Tatlow, Journal of the Chemical Society (1965)
6336–6342.
[17] R.D. Chambers, F.D. Drakesmith, W.K.R. Musgrave, Journal of the Chemical Society
(1965) 5045–5048.
(b) X. Huang, H.R. Heulings, V. Le, J. Li, Chemistry of Materials 13 (2001)
3754–3759;
[18] R.D. Chambers, J. Hutchinson, W.K.R. Musgrave, Journal of the Chemical Society
(1964) 3573–3576.
(c) X. Huang, J. Li, H. Fu, Journal of the American Chemical Society 122 (2000)
8789–8790;
[19] G.M. Sheldrick, Acta Crystallographica A 64 (2008) 112–122.
[20] (a) A.L. Spek, PLATON,
A Multipurpose Crystallographic Tool, Version 10M,
(d) S.Y. Girgis, A.M. Salem, M.S. Selim, Journal of Physics B 19 (2007) 116213/1.
[10] P.L. Coe, A.J. Rees, Journal of Fluorine Chemistry 101 (2000) 45–60.
[11] (a) J.T. Ayers, S.R. Anderson, Synthetic Communications 29 (1999)
351–358;
Utrecht University, The Netherlands, 2003;
(b) A.L. Spek, Journal of Applied Crystallography 36 (2003) 7–13.
[21] C.F. Macrae, P.R. Edgington, P. McCabe, E. Pidcock, G.P. Shields, R. Taylor, M.
Towler, J. van de Stree, Journal of Applied Crystallography 39 (2006) 453–457.